Key residues involved in the interaction between chlorpyrifos and a chemosensory protein in Rhopalosiphum padi: Implication for tracking chemical residues via insect olfactory proteins.

The development of advanced biosensors for tracking chemical residues and detecting environmental pollution is of great significance. Insect chemical sensory proteins, including chemosensory proteins (CSPs), are easy to synthesize and purify and have been used to design proteins for specific biosensor applications. Chlorpyrifos is one of the most commonly used chemicals for controlling insect pests in agriculture. This organophosphate is harmful to aquatic species and has long-term negative consequences for the ecosystem. CSPs can bind and carry a variety of environmental chemicals, including insecticides. However, the mechanism by which CSPs bind to insecticides in aphids has not been clarified. In this study, we discovered that RpCSP1 from Rhopalosiphum padi has a higher affinity for chlorpyrifos, with a Ki value of 4.763 ± 0.491 µM. Multispectral analysis revealed the physicochemical binding mechanism between RpCSP1 and chlorpyrifos. Computational simulation analysis demonstrated that the main factor promoting the development of the RpCSP1-chlorpyrifos complex is polar solvation energy. Four residues (Arg33, Glu94, Gln145, Lys153) were essential in facilitating the interaction between RpCSP1 and chlorpyrifos. Our research has improved knowledge of the relationship between CSPs and organophosphorus pesticides. This knowledge contributes to the advancement of biosensor chips for tracking chemical residues and detecting environmental pollution through the use of CSPs.

MOF-derived sandwich-structured dual Z-Scheme Co9S8@ZnIn2S4/CdSe hollow nanocages heterojunction: Target-induced ultrasensitive photoelectrochemical sensing of chlorpyrifos.

Exploring efficient photoactive material presents an intriguing opportunity to enhance the analytical performance of photoelectrochemical (PEC) sensor in the environmental analysis. In this work, a sandwich-structured multi-interface Co9S8@ZnIn2S4/CdSe QDs dual Z-Scheme heterojunction, derived from metal-organic framework (MOF), was synthesized as a sensing platform for chlorpyrifos detection, by integrating with enzyme-induced in situ insoluble precipitates strategy. The meticulously designed Co9S8@ZnIn2S4/CdSe QDs exhibited enhanced charge separation efficiency and was proved to be a highly effective sensing platform for the immobilization of biomolecules, attributing to the intrinsic dual Z-Scheme heterojunction and the distinctive hollow structure. The proposed PEC sensing platform combined with enzyme-induced in situ precipitate signal amplification strategy achieved superior performance for sensing of chlorpyrifos (CPF), showing in wide linear range (1.0 pg mL-1-100 ng mL-1), with a limit of detection (0.6 pg mL-1), excellent selectivity, and stability. This work offers valuable insights for the design of novel advanced photoactive materials aimed at detecting environmental pollutants with low level concentration.

Validation of Salamander Dermal Mucus Swabs as a Novel, Nonlethal Approach for Amphibian Metabolomics and Glutathione Analysis Following Pesticide Exposure.

Evaluating biomarkers of stress in amphibians is critical to conservation, yet current techniques are often destructive and/or time-consuming, which limits ease of use. In the present study, we validate the use of dermal swabs in spotted salamanders (Ambystoma maculatum) for biochemical profiling, as well as glutathione (GSH) stress response following pesticide exposure. Thirty-three purchased spotted salamanders were acclimated to laboratory conditions at Washington College (Chestertown, MD, USA) for 4 weeks. Following acclimation, salamanders were randomly sorted into three groups for an 8-h pesticide exposure on soil: control with no pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), or chlorpyrifos. Before and after exposure, mucus samples were obtained by gently rubbing a polyester-tipped swab 50 times across the ventral and dorsal surfaces. Salamanders were humanely euthanized and dissected to remove the brain for acetylcholinesterase and liver for GSH and hepatic metabolome analyses, and a whole-body tissue homogenate was used for pesticide quantification. Levels of GSH were present in lower quantities on dermal swabs relative to liver tissues for chlorpyrifos, 2,4-D, and control treatments. However, 2,4-D exposures demonstrated a large effect size increase for GSH levels in livers (Cohen's d = 0.925, p = 0.036). Other GSH increases were statistically insignificant, and effect sizes were characterized as small for 2,4-D mucosal swabs (d = 0.36), medium for chlorpyrifos mucosal swabs (d = 0.713), and negligible for chlorpyrifos liver levels (d = 0.012). The metabolomics analyses indicated that the urea cycle, alanine, and glutamate metabolism biological pathways were perturbed by both sets of pesticide exposures. Obtaining mucus samples through dermal swabbing in amphibians is a viable technique for evaluating health in these imperiled taxa. Environ Toxicol Chem 2024;43:1126-1137. © 2024 SETAC.

Contaminant dynamics in honey bees and hive products of apiaries from environmentally contrasting Argentinean regions.

Argentina is a leading honey producer and honey bees are also critical for pollination services and wild plants. At the same time, it is a major crop producer with significant use of insecticides, posing risks to bees. Therefore, the presence of the highly toxic insecticide chlorpyrifos, and forbidden contaminants (organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)) was investigated in honey bee, beebread, wax and honey samples in apiaries from three contrasting regions of Argentina. Chlorpyrifos was detected in all samples with higher levels during period 1 (spring) in contrast to period 2 (fall), agreeing with its season-wise use in different crops, reaching 3.05 ng/g in honey bees. A subsequent first-tier pesticide hazard analysis revealed that it was relevant to honey bee health, mainly due to the high concentrations found in wax samples from two sites, reaching 132.4 ng/g. In addition, wax was found to be the most contaminated matrix with a prevalence of OCPs (∑OCPs 58.23-172.99 ng/g). Beebread samples showed the highest concentrations and diversity of pesticide residues during period 1 (higher temperatures). A predominance of the endosulfan group was registered in most samples, consistent with its intensive past use, especially in Central Patagonia before its prohibition. Among the industrial compounds, lighter PCB congeners dominated, suggesting the importance of atmospheric transport. The spatio-temporal distribution of pesticides shows a congruence with the environmental characteristics of the areas where the fields are located (i.e., land use, type of productive activities and climatic conditions). Sustained monitoring of different pollutants in beekeeping matrices is recommended to characterize chemical risks, assess the health status of honey bee hives and the pollution levels of different agroecosystems. This knowledge will set a precedent for South America and be helpful for actions focused on the conservation of pollination services, apiculture and ecosystems in Argentina.

Proximal discrepancies in intrinsic atomic interaction determines comparative in vivo biotoxicity of Chlorpyrifos and 3,5,6-trichloro-2-pyridinol in embryonic zebrafish.

Bioaccumulation of Chlorpyrifos (CP) as pesticides due to their aggrandized use in agriculture has raised serious concern on the health of ecosystem and human beings. Moreover, their degraded products like 3,5,6-trichloro-2-pyridinol (TCP) has enhanced the distress due to their unpredictable biotoxicity. This study evaluates and deduce the comparative in vivo mechanistic biotoxicity of CP and TCP with zebrafish embryos through experimental and computational approach. Experimental cellular and molecular analysis showed higher induction of morphological abnormalities, oxidative stress and apoptosis in TCP exposed embryos compared to CP exposure due to upregulation of metabolic enzymes like Zhe1a, Sod1 and p53. Computational analysis excavated the differential discrepancies in intrinsic atomic interaction as a reason of disparity in biotoxicity of CP and TCP. The mechanistic differences were deduced due to the differential accumulation and internalisation leading to variable interaction with metabolic enzymes for oxidative stress and apoptosis causing physiological and morphological abnormalities. The study unravelled the information of in vivo toxicity at cellular and molecular level to advocate the attention of taking measures for management of CP as well as TCP for environmental and human health.

Investigating the prevalence of erectile dysfunction among men exposed to organophosphate insecticides.

INTRODUCTION: Erectile dysfunction (ED) poses a significant disease morbidity and contributor to male infertility, where an estimated 20-40% of men are affected annually. While several risk factors have been identified in the etiology of ED (e.g., aging, heart disease, diabetes, and obesity), the complete pathogenesis remains to be elucidated. Over the last few decades, the contribution of environmental exposures to the pathogenesis of ED has gained some attention, though population studies are limited and results are mixed. Among environmental contaminants, organophosphate (OP) insecticides represent one of the largest chemical classes, and chlorpyrifos is the most commonly used OP in the U.S. OP exposure has been implicated in driving biological processes, including inflammation, reactive oxygen species production, and endocrine and metabolism disruption, which have been demonstrated to adversely affect the hypothalamus and testes and may contribute to ED. Currently, studies evaluating the association between OPs and ED within the U.S. general population are sparse. METHODS: Data were leveraged from the National Health and Nutrition Examination Survey (NHANES), which is an annually conducted, population-based cross-sectional study. Urinary levels of 3,5,6-trichloro-2-pyridinol (TCPy), a specific metabolite of the most pervasive OP insecticide chlorpyrifos, were quantified as measures of OP exposure. ED was defined by responses to questionnaire data, where individuals who replied "sometimes able" or "never able" to achieve an erection were classified as ED. Chi-square, analysis of variance (ANOVA), and multivariable, weighted linear and logistic regression analyses were used to compare sociodemographic variables between quartiles of TCPy exposure, identify risk factors for TCPy exposure and ED, and to analyze the relationship between TCPy and ED. RESULTS: A total of 671 adult men were included in final analyses, representing 28,949,379 adults after survey weighting. Approximately 37% of our cohort had ED. Smoking, diabetes, aging, Mexican-American self-identification, and physical inactivity were associated with higher ED prevalence. Analysis of TCPy modeled as a continuous variable revealed nonsignificant associations with ED (OR = 1.02 95% CI [0.95, 1.09]). Stratification of total TCPy into quartiles revealed increased odds of ED among adults in the second and fourth quartiles, using the first quartile as the reference (OR = 2.04 95% CI [1.11, 3.72], OR = 1.51 95% CI [0.58, 3.93], OR = 2.62 95% CI [1.18, 5.79], for quartiles 2, 3, and 4, respectively). CONCLUSIONS: The results of our study suggest a potential role for chlorpyrifos and other OPs the pathogenesis of ED. Future studies are warranted to validate these findings, determine clinical significance, and to investigate potential mechanisms underlying these associations.

Preparation of a magnetic molecularly imprinted polymer on fibrous silica nanosphere via self-polycondensation for micro solid-phase extraction of chlorpyrifos.

Throughout this research, a new magnetic molecularly imprinted polymer on fibrous silica nanosphere was prepared through self-polycondensation. The selective extraction of chlorpyrifos was performed by the synthesized sorbent and as a determination system, a gas chromatography-electron capture was applied. The formation of sorbent was confirmed through the use of Fourier transform infrared spectroscopy and field emission scanning electron microscopy techniques. The parameters affecting the extraction efficacy of the proposed method were scrutinized in an optimized way. The linear range and the detection limit of the studied method were 0.003-0.3 and 0.001 ng mL-1, respectively. The relative standard deviations were 4.1-5.2 and 5.6-7.6 % for intra- and inter-day (n = 3), respectively. To assess the performance of the proposed method, some water and fruit samples were analyzed and the extraction recoveries of 83-109 % were obtained. These results revealed the method's performance in the analysis of chlorpyrifos in real samples.

Residue behaviour and health risk assessment of chlorpyrifos and mancozeb in apple fruits and soil.

Mancozeb residue estimation was done using second derivative ultraviolet spectroscopy by Shimadzu ultraviolet-visible spectrophotometer, and chlorpyrifos was estimated by QuEChERS technique using GC-FPD. The persistence for chlorpyrifos was carried out at two locations, and for mancozeb, persistence studies were carried out at four locations. Initial deposits of mancozeb on apple fruits ranged from 1.33 to 1.63 mg/kg at the recommended dose and from 2.55 to 3.26 mg/kg at double the recommended dose at all four locations. Chlorpyrifos residues in apple fruits had an initial deposit of 0.94-0.99 mg/kg at recommended dose and 1.75-1.92 mg/kg at double the recommended dose. Mancozeb residues in apple fruit were below the detection limit (BDL) after 20 days at recommended dose and after 25 days at double the recommended dose at two locations, while mancozeb residue at the other two locations and the residues of chlorpyrifos at all locations reached BDL after 15 and 20 days at recommended and double the recommended doses, respectively. Half-life of mancozeb varied from 3.07 to 4.02 days at recommended dose and from 3.30 to 4.32 days at double the recommended dose, whereas chlorpyrifos residues dissipated to half their initial concentration on 2.33-2.35 days at recommended dose and 2.89-2.90 days at double the recommended dose. The soil samples showed no presence of residues of chlorpyrifos and mancozeb at harvest. The risk assessment revealed that hazard quotient for the intake of mancozeb was in the range of 0.06-0.13% and 0.20-0.44% for rural and urban population, while for the intake of chlorpyrifos, hazard quotient was in the range of 0.10-0.12% for rural population and 0.33-0.38% for urban population, and theoretical maximum dietary intake (9.67 × 10-5 mg/person and 3.18 × 10-4 mg/person for rural population and urban population in case of mancozeb and 3.22 × 10-5 mg/person and 1.06 × 10-4 mg/person for rural population and urban population in case of chlorpyrifos) was also found to be less than maximum permissible intake (1.38 mg/kg for mancozeb and 0.60 mg/kg for chlorpyrifos). The results of risk assessment thereby indicated that apple consumption does not pose a risk to human health.

SERS combined with QuEChERS using NBC and Fe3O4 MNPs as cleanup agents to rapidly and reliably detect chlorpyrifos pesticide in citrus.

The surface-enhanced Raman spectroscopy (SERS) technique is being increasingly used for the detection of pesticide residues in agricultural products. However, there are large amounts of fluorescence-producing substances in agricultural products, which seriously affect the Raman signal of the analyte. In this paper, the QuEChERS method was used to remove interfering fluorescent substances in the analyte, and the purification effects of different doses of nano bamboo charcoal (NBC) and Fe3O4 magnetic nanoparticle (Fe3O4 MNP) adsorbents were studied. Meanwhile, the Raman spectral acquisition conditions (AuNPs, test solution, and NaCl) were optimized based on the orthogonal test method. The results showed that 300 µL AuNPs, 40 µL test solution, and 100 µL 1.5% NaCl gave the best SERS response effect. 12.5 mg NBC combined with 10 mg Fe3O4 MNPs could effectively remove the interfering substances from citrus. The Raman spectra of chlorpyrifos molecules were theoretically modeled using density-functional theory (DFT). By comparing the DFT results with the actual tests, five feature peaks, at 338, 522, 558, 672, and 1600 cm-1, were obtained for the detection of chlorpyrifos pesticide residues in citrus. Based on the Raman feature peak intensity at 672 cm-1, the concentration of chlorpyrifos in citrus showed a good linear relationship (R2 = 0.9979) in the concentration range of 3-20 mg kg-1. The recovery rate was 92.12% to 98.38%, and the relative standard deviation (RSD) was 1.77% to 5.29%. The lowest detection concentration was about 3 mg kg-1, and the detection time of a single sample could be completed within 15 min. This study showed that the combination of SERS and QuEChERS preprocessing methods could achieve rapid detection of chlorpyrifos pesticide residues in citrus.

The concentration of pesticides in tomato: a global systematic review, meta-analysis, and health risk assessment.

To improve farming productivity, a large number of pesticides have been used worldwide in recent decades, leading to the pollution of soil, agri-products, and water, directly/indirectly affecting human health. In this regard, many studies were conducted in different countries on residual pesticides in the environment. In the current study, residual pesticides including chlorpyrifos, cypermethrin, diazinon, malathion, and metalaxyl in tomatoes were meta-analyzed and health risk of consumers was estimated. For this purpose, based on a systematic review, data from 47 studies were extracted and meta-analyzed, and the health impact of pooled concentrations was assessed via a health risk method. According to the results, metalaxyl had the most concentration followed by malathion, cypermethrin, diazinon, and chlorpyrifos, respectively. The non-carcinogenic risk (n-CR) was calculated from crop consumption also showed that exposure to malathion has the most risk. Among the investigated communities, Iranian consumers were in considerable health risk (THQ > 1). Considering that the potential for the use of pesticides will increase with the need for food in the future, hence, governments must manage the usage by governments via alternative methods such as cultural, biological, physical, and genetic modifications.

Pesticides residues determination and probabilistic health risk assessment in the soil and cantaloupe by Monte Carlo simulation: A case study in Kashan and Aran-Bidgol, Iran.

Cantaloupe is a popular agricultural product in the hot season of Iran. On the other hand, the frequent use of pesticides in cantaloupe fields is the most important threat to the health of farmers and consumers. Therefore, the present study aims to measure the concentration of diazinon (DZN), chlorpyrifos (CPF), and malathion (MLT) in cantaloupe cultivated in Kashan and Aran-Bidgol (Iran) and to estimate the possible oral and dermal risk of these pesticides by Monte Carlo simulation (MCS). 36 cantaloupe samples, 18 samples before, and 18 samples after the latent period were collected from different places of cantaloupe cultivation from April to May 2021. After measuring the pesticides using the QuEChERS approach, oral and dermal risk assessments were calculated.The mean and standard deviation of the concentrations of chlorpyrifos, malathion, and diazinon in 18 cantaloupe samples, after the latent period, were (30.39 ± 13.85), (18.361 ± 1.8), and (21.97 ± 0.86) µg kg-1, respectively. Concentration of Malathion, diazinon, and Chlorpyrifos in the soil were 0.22, 0.25, and 0.3 mg kg-1, respectively, and pesticide cumulative risk assessment in soil was obtained 0.011 for Malathion, 0.05 for diazinon and 0.03 for Chlorpyrifos. Target Hazard Quotient (THQ) according to the cantaloupe consumption and dermal exposure in children and adults, was safe range. Although non-cancerous dermal and oral risk of cantaloupe is low, constant exposure can be harmful. Therefore, the findings of this study play an important role in increasing the understanding of the negative health consequences of pesticide contamination in cantaloupe for consumers, especially local residents, and can help by adopting remedial strategies to reduce environmental concerns.

Cumulative health risk assessment of pesticide residues in apple products in the Northwest of Iran using Monte Carlo simulation.

Pesticide residues in fruits and vegetables cause serious health issues, especially among children. This research was carried out to monitor and evaluate the risks of organophosphate pesticide residues in Maragheh County apple products from 2020. The Monte Carlo Simulation approach (MCS) was used to evaluate the non-cancerous effects of exposure to pesticide residues in adults and children. Apple samples were taken every two weeks at the Maragheh central market during the summer and fall months. In this study, seventeen pesticide residues in 30 apple samples were estimated using a modified QuECheRS extraction technique coupled with GC/MS. Of the seventeen organophosphate pesticides, thirteen were identified as pesticide residues (76.47%). The highest concentration found in the apple samples was associated with chlorpyrifos pesticide at 1.05 mg/kg. Pesticide residues exceeding the maximum residue limits (MRLs) were found in 100% of apple specimens, and more than 75% of the samples contained ten or more pesticide residues. Approximately 45%-80% of pesticide residues on apple samples were removed after washing and peeling. Chlorpyrifos pesticide had the highest health quotient (HQ) for men, women, and children with values of 0.046, 0.054, and 0.23, respectively. Cumulative risk assessment (CRA) of non-carcinogenic effects indicates that there is no significant health risk in the adult age group from apple consumption (HI < 1). Nevertheless, children are at high non-cancer risk from eating unwashed apples (HI = 1.3). This finding shows that high levels of pesticide residues in apple samples, especially unwashed apples, can be a serious concern for the health of children. To better protect consumer health, continuous and regular monitoring, strict regulations, training, and awareness of farmers, especially control pre-harvest interval (PHI) is recommended.

An interference-free SERS-based aptasensor for chlorpyrifos detection.

In this study, we propose an interference-free SERS-based aptasensor for trace detection of chlorpyrifos (CPF) in real samples. In the aptasensor, gold nanoparticles coated with Prussian blue (Au@PB NPs) were employed as SERS tags to provide a sole and intense Raman emission at 2160 cm-1, which could avoid overlapping with the Raman spectrum of the real samples in 600-1800 cm-1 to improve the anti-matrix effect ability of the aptasensor. Under the optimum conditions, this aptasensor displayed a linear response for CPF detection in the range of 0.1-316 ng mL-1 with a low detection limit of 0.066 ng mL-1. In addition, the prepared aptasensor shows excellent application to determine CPF in cucumber, pear and river water samples. The recovery rates were highly correlated with high-performance liquid chromatography‒mass spectrometry (HPLC‒MS/MS). This aptasensor shows interference-free, specific and sensitive detection for CPF and offers an effective strategy for other pesticide residue detection.

Pesticide Exposure among Latinx Children in Rural Farmworker and Urban Non-Farmworker Communities: Associations with Locality and Season.

This study uses repeated measures to document the pesticide exposure of rural and urban Latinx children (age eight at baseline), and to compare these children in terms of the frequency and concentration of their exposure to a large set of pesticides, accounting for season. We used silicone wristbands worn for one week up to ten times at quarterly intervals from 2018 to 2022 to assess pesticide exposure in children from rural farmworker (n = 75) and urban non-farmworker (n = 61) families. We determined the detection and concentrations (ng/g) of 72 pesticides and pesticide degradation products in the wristbands using gas chromatography electron capture detection and gas chromatography mass spectrometry. The most frequently detected pesticide classes were organochlorines, pyrethroids, and organophosphates. Controlling for season, organochlorine or phenylpyrazole detections were less likely for rural children than for urban children. Detections of organochlorines, pyrethroids, or organophosphates were lower in spring and summer versus winter. Controlling for season, urban children had greater concentrations of organochlorines, while rural children had greater concentrations of pyrethroids and Chlorpyrifos. Pesticide concentrations were lower in winter and spring compared with summer and fall. These results further document that pesticides are ubiquitous in the living environment for children in vulnerable, immigrant communities.

Quantification of Chlorpyrifos Residues in Water under Thermodynamically Favorable Electrodics Using the f-MWCNT/N-(2-C2H5O) ED(CH3COONa)3 Composite of Superior Selectivity.

Researchers are continually seeking potential alternatives to develop water quality sensors with higher selectivity to obtain the desired performance during real-time deployment. Quantification technologies involving interface materials of distinguishing capacity at elevated matrix complexity are desirable. However, there remains a challenge in designing suitable techniques, methodologies, and appropriate validations to support the grounds for the selection of interface materials of enhanced selectivity. The ability to monitor chlorpyrifos in analytical and commercial grade compounds and in the water matrix using an interface material of suitable states is the focus of this work. Herein, N-(2-hydroxyethyl) ethylenediamine triacetic acid trisodium (N-(2-C2H5O) ED(CH3COONa)3) incorporated with functionalized multiwalled carbon nanotube (f-MWCNT) is reported to provide thermodynamically favorable charge transfer for the quantification of chlorpyrifos residues under varying internal and external conditions with appropriate validations using density functional theory (DFT) and high-performance liquid chromatography (HPLC). The sensor exhibited excellent figures of merit such as limit of detection (LOD) and limit of quantitation (LOQ) of 9.7 pM and 29.4 pM, respectively.

Pesticides exposure in pregnant Argentinian women: Potential relations with the residence areas and the anthropometric neonate parameters.

Intrauterine environment is the first chemical exposure scenario in life, through transplacental transfer. In this study, the aim was to determine concentrations of organochlorine pesticides (OCPs) and selected current use pesticides in the placentas of pregnant women from Argentina. Socio-demographic information, the mother's lifestyle and neonatal characteristics were also analysed and related to pesticides residue concentrations. Thus, 85 placentas were collected at birth, from an area of intensive fruit production for the international market, in Patagonia Argentina. Concentrations of 23 pesticides including, trifluralin (herbicide), the fungicides chlorothalonil and HCB, and the insecticides chlorpyrifos, HCHs, endosulfans, DDTs, chlordanes, heptachlors, drins and metoxichlor, were determined by GC-ECD and GC-MS. Results were first analysed all together and then grouped by their residential settings, in urban and rural groups. Total mean pesticide concentration was 582.6 ± 1034.4 ng/g lw, where DDTs (325.9 ± 950.3 ng/g lw) and chlorpyrifos (188.4 ± 365.4 ng/g lw) showed a high contribution. Pesticide levels found exceeded those reported in low, middle and high income countries from Europe, Asia and Africa. In general, pesticides concentrations were not associated with neonatal anthropometric parameters. When the results were analysed by residence place, significantly higher concentrations of total pesticides and chlorpyrifos (Mann Whitney test p = 0.0003 and p = 0.032, respectively) were observed in placentas collected from mothers living in rural settings compared to urban areas. Rural pregnant women presented the highest pesticide burden (5.9 µg), where DDTs and chlorpyrifos were the major constituents. These results suggested that all pregnant women are highly exposed to complex pesticide mixtures, including banned OCPs and the widely used chlorpyrifos. Based on the pesticide concentrations found, our results warn of possible health impacts from prenatal exposure through transplacental transfer. This is one of the first reports of both chlorpyrifos and chlorothalonil concentrations in placental tissue, and contributes to the knowledge of current pesticide exposure in Argentina.

Ecological risk assessment of pesticides on soil biota: An integrated field-modelling approach.

Pesticide residues in soils can cause negative impacts on soil health as well as soil biota. However, research related to the toxicity and exposure risks of pesticides to soil biota are scarce, especially in the North China Plain (NCP) where pesticides are intensively applied. In this study, the occurrence and distribution of 15 commonly used pesticides in 41 fields in Quzhou county in the NCP were determined during the growing season in 2020. The ecological risks of pesticides to the soil biota, including earthworms, enchytraeids, springtails, mites and nitrogen mineralization microorganisms, were assessed using toxicity exposure ratios (TERs) and risk quotient (RQ) methods. Based on pesticide detection rates and RQs, pesticide hazards were ranked using the Hasse diagram. The results showed that pesticides were concentrated in the 0-2 cm soil depth. Chlorantraniliprole was the most frequently detected pesticide with a detection rate of 37%, while the highest concentration of 1.85 mg kg-1 was found for carbendazim in apple orchards. Chlorpyrifos, carbendazim and imidacloprid posed a chronic exposure risk to E. fetida, F. candida and E. crypticus with the TERs exceeding the trigger value. Pesticide mixtures posed ecological risks to soil biota in 70% of the investigated sites. 47.5% of samples were ranked as high-risk, with the maximum RQ exceeding 490. According to the Hasse diagram, abamectin, tebuconazole, chlorantraniliprole and chlorpyrifos were ranked as the most hazardous pesticides for soil biota in the study region, indicating that alternative methods of pest management need to be considered. Therefore, practical risk mitigation solutions are recommended, in which the use of hazardous pesticides would be replaced with low-risk pesticides with similar functions from the Hasse diagram, or with biopesticides.

Isolation of organophosphate pesticides from water using gold nanoparticles doped magnetic three-dimensional graphene oxide.

Pesticides are a large group of pristine organic contaminants, which are widely discharged into environmental water due to agricultural activities. Hence, extraction, determination, and removal of pesticides from water resources are necessary for human health. In this study, novel adsorbent was developed based on three-dimensional magnetic graphene coated with gold nanoparticles (3D-MG@AuNPs) for extraction of chlorpyrifos, dicrotophos, fenitrothion, and piperophos as four specific organophosphorus pesticides (OPPs) from wastewater and tap water samples. The proposed nanocomposite was characterized; FTIR and EDX are performed for the expected functional groups and elemental analysis, SEM showed the unique and spherical AuNPs are well dispersed over graphene sheets. In this investigation, the important parameters that have effect on the extraction efficiency, including the desorbing solvent, desorbing solvent volume, vortex time, the extraction time, adsorbent dosage, pH of sample solutions, and salt effect were evaluated. In conclusion, the measured amounts of the chosen OPPs were determined using the gas chromatography microelectron capture (µECD-GC) method. Limits of quantification (S/N ratio of 10) and detection (S/N ratio of 3) were attained at concentrations of 0.26-0.43 µg.L-1 and 0.08-0.14 µg.L-1, respectively. According to the results of the investigations, the synthesized 3D-MG@AuNPs did not require any complicated sample preparation methods; therefore, it is a very good choice for solid magnetic phase extraction studies.

Magnetic Relaxation Switching Immunosensors via a Click Chemistry-Mediated Controllable Aggregation Strategy for Direct Detection of Chlorpyrifos.

Chlorpyrifos (CPF) is the most frequently found organophosphate pesticide residue in solid food samples and can cause increasing public concerns about potential risks to human health. Traditional detection signals of such small molecules are mostly generated by target-mediated indirect conversion, which tends to be detrimental to sensitivity and accuracy. Herein, a novel magnetic relaxation switching detection platform was developed for target-mediated direct and sensitive detection of CPF with a controllable aggregation strategy based on a bioorthogonal ligation reaction between tetrazine (Tz) and trans-cyclooctene (TCO) ligands. Under optimal conditions, this sensor can achieve a detection limit of 37 pg/mL with a broad linear range of 0.1-500 ng/mL in 45 min, which is approximately 51-fold lower than that of the gas chromatography analysis and 13-fold lower than that of the enzyme-linked immunosorbent assay. The proposed click chemistry-mediated controllable aggregation strategy is direct, rapid, and sensitive, indicating great potential for residue screening in food matrices.

Chitosan oligosaccharide alleviates and removes the toxicological effects of organophosphorus pesticide chlorpyrifos residues.

The abuse of chlorpyrifos (CHP), a commonly used organophosphorus pesticide, has caused many environmental pollution problems, especially its toxicological effects on non-target organisms. First, CHP enriched on the surface of plants enters ecosystem circulation along the food chain. Second, direct inflow of CHP into the water environment under the action of rainwater runoff inevitably causes toxicity to non-target organisms. Therefore, we used rats as a model to establish a CHP exposure toxicity model and studied the effects of CHP in rats. In addition, to alleviate and remove the injuries caused by residual chlorpyrifos in vivo, we explored the alleviation effect of chitosan oligosaccharide (COS) on CHP toxicity in rats by exploiting its high water solubility and natural biological activity. The results showed that CHP can induce the toxicological effects of intestinal antioxidant changes, inflammation, apoptosis, intestinal barrier damage, and metabolic dysfunction in rats, and COS has excellent removal and mitigation effects on the toxic damage caused by residual CHP in the environment. In summary, COS showed significant biological effects in removing and mitigating blood biochemistry, antioxidants, inflammation, apoptosis, gut barrier structure, and metabolic function changes induced by residual CHP in the environment.